JP6939804B2 - Compositions, hole transport material compositions, and ink compositions - Google Patents

Description

Embodiments of the present invention relate to compositions, hole transport material compositions, and ink compositions. In addition, another embodiment of the present invention relates to an organic layer and a method for producing an organic layer using a composition, a hole transport material composition, or an ink composition. Further, another embodiment of the present invention relates to an organic electronics element having an organic layer and an organic electroluminescence element (hereinafter, also referred to as an organic EL element). Furthermore, another embodiment of the present invention relates to a display element, a lighting device, and a display device using an organic EL element.

An organic electronics element is an element that performs an electrical operation using an organic substance. Organic electronic devices are expected to be able to exhibit features such as energy saving, low price, and high flexibility, and are attracting attention as a technology to replace conventional inorganic semiconductors mainly composed of silicon.

Among organic electronic devices, organic EL devices are attracting attention as large-area solid-state light source applications as alternatives to incandescent lamps or gas-filled lamps, for example. It is also attracting attention as the most promising self-luminous display that can replace the liquid crystal display (LCD) in the flat panel display (FPD) field, and its commercialization is progressing.

Organic EL elements are roughly classified into two types, low-molecular-weight organic EL elements and high-molecular-weight organic EL elements, depending on the organic material used. As the organic material, a low-molecular-weight material is used in the low-molecular-weight organic EL element, and a high-molecular-weight material is used in the high-molecular-weight organic EL element. Compared with the low molecular weight organic EL element which mainly forms a film in a vacuum system, the polymer type organic EL element enables simple film formation by plate printing or inkjet. Therefore, the polymer-type organic EL element is expected as an indispensable element for future large-screen organic EL displays.

In recent years, in both low-molecular-weight organic EL devices and high-molecular-weight organic EL devices, in order to improve device characteristics such as luminous efficiency and device life, the organic layers constituting the organic EL device have been multi-layered.

In a small molecule organic EL device, a film is generally formed by a thin film deposition method, so that multi-layering can be easily achieved by sequentially changing the compounds used for vapor deposition. On the other hand, in the polymer type organic EL element, it is difficult to increase the number of layers. The reason is that in the polymer type organic EL element, the film is formed by a wet process such as plate printing or inkjet, so that the lower layer formed earlier is dissolved when the upper layer is formed. In order to increase the number of layers of the polymer-type organic EL device, a method is desired in which the lower layer that has already been formed does not change when the upper layer is formed.

As a method for realizing the multi-layered structure of the polymer-type organic EL element, studies using the reaction of the compound have been made (see, for example, Patent Document 1, Patent Document 2, and Non-Patent Document 1). These documents disclose a method of multi-layering by reacting a polymerizable substituent introduced into a compound. For example, it is multi-layered using a polymerization reaction such as a silyl group, a styryl group, an oxetane group, or an acrylic group, or multi-layered using a dimerization such as a trifluorovinyl ether group or a benzocyclobutene group.

Japanese Unexamined Patent Publication No. 2004-199935 International Publication No. 2005/053056

Carlos A. Zuniga, Stephen Barlow, and Seth R. Marder, "Approaches to Solution-Processed Multilayer Organic Light-Emitting Diodes Based on Cross-Linking", Chem. Mater., 2011, 23 (3), pp 658-681

An object of the present invention is to provide a composition, a hole transport material composition, and an ink composition, which enable a multi-layered organic layer by a coating method and are useful for improving the characteristics of an organic electronic device. And. Another object of the present invention is to provide an organic layer and a method for producing an organic layer, which can be multi-layered by a coating method and which is useful for improving the characteristics of an organic electronic device. .. Another embodiment of the present invention aims to provide an organic electronic device and an organic EL device having excellent characteristics. Furthermore, another embodiment of the present invention aims to provide a display element, a lighting device, and a display device having excellent characteristics.

An embodiment of the present invention contains a polymer or oligomer (A) and an initiator (B), and the polymer or oligomer (A) comprises a structural unit containing an aromatic amine structure and a structural unit containing a carbazole structure. It contains at least one selected from the above and a structural unit containing a thienyl group which may have a substituent at one or more terminals, and does not contain an alkyl group having 5 or more carbon atoms. With respect to compositions in which the solubility is altered by the addition of light, or both heat and light.

（式（Ｉａ）及び式（Ｉｂ）中のＲ^１〜Ｒ^３は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ^１〜Ｒ^３の少なくとも２つは水素原子である。）In the composition, preferably, the thienyl group contains at least one selected from the group consisting of the structure represented by the following formula (Ia) and the structure represented by the formula (Ib).

^{(R 1 to} R ³ in the formula (Ia) and the formula (Ib) independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least two of ^{R 1 to} R ^{3 are hydrogen atoms.} be.)

The aromatic amine structure and the carbazole structure are, for example, unsubstituted or have an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

Preferably, the polymer or oligomer (A) has a branched structure, has three or more ends, and has three or more thienyl groups at all ends.

In any of the compositions, the initiator (B) preferably comprises an oxidizing agent.

In any of the compositions, the initiator (B) preferably comprises an onium salt.

The weight average molecular weight of the polymer or oligomer (A) is, for example, 1,000 to 1,000,000.

Any of the above compositions may further contain the solvent (C).

In any one of the compositions, the surface free energy expressed as the sum of two components of the polar component and a nonpolar component by Owens-We n dt method of the polymer or oligomer (A) is preferably from 41 mJ / ^{m 2} or more Is.

Another embodiment of the present invention relates to a hole transport material composition containing any of the above compositions.

Further, another embodiment of the present invention relates to an ink composition containing any of the above compositions.

Other embodiments of the present invention are formed by applying any of the above compositions, said hole transport material compositions, or said ink compositions and applying heat, light, or both heat and light. Regarding the organic layer.

Further, still another embodiment of the present invention is a step of applying the composition, the hole transport material composition, or the ink composition to form a coating layer, and the coating layer. The present invention relates to a method for producing an organic layer, which comprises a step of applying heat, light, or both heat and light.

Another embodiment of the present invention relates to an organic electronics element and an organic electroluminescence element having at least one of the organic layers. In a preferred embodiment, the organic electroluminescence device further comprises a flexible substrate. In a preferred embodiment, the organic electroluminescence device further comprises a resin film substrate.

Further, another embodiment of the present invention relates to a display element and a lighting device provided with any of the above-mentioned organic electroluminescence elements, and a display device including the lighting device and a liquid crystal element as a display means.

According to an embodiment of the present invention, it is possible to provide a composition, a hole transport material composition, and an ink composition which enable multi-layering of an organic layer by a coating method and are useful for improving the characteristics of an organic electronic device. Can be done. Further, according to another embodiment of the present invention, it is possible to provide an organic layer and a method for producing an organic layer, which can be multi-layered by a coating method and which is useful for improving the characteristics of an organic electronic device. .. Further, according to another embodiment of the present invention, it is possible to provide an organic electronic device and an organic EL device having excellent characteristics. Further, according to another embodiment of the present invention, it is possible to provide a display element, a lighting device, and a display device having excellent characteristics.

It is sectional drawing which shows an example of the organic EL element which is an embodiment of this invention.

Embodiments of the present invention will be described below.
<Composition>
The composition according to the embodiment of the present invention is a composition containing a polymer or oligomer (A) and an initiator (B), and the solubility is changed by applying heat, light, or both heat and light. ..

[Polymer or oligomer (A)]
The polymer or oligomer (A) (hereinafter, may be referred to as "polymer (A)") is selected from at least a group consisting of a structural unit containing an aromatic amine structure and a structural unit containing a carbazole structure in the molecule. A structural unit containing one type and having a thienyl group which may have a substituent at one or more ends of the polymer (A) is contained. The polymer (A) does not contain an alkyl group having 5 or more carbon atoms in the molecule. The "alkyl group having 5 or more carbon atoms" means an alkyl group having 5 or more carbon atoms, which may be linear, cyclic or branched and has no substituent.

The polymer (A) may be a linear polymer or a branched polymer having a branched structure. The linear polymer (A) contains a divalent structural unit and a monovalent structural unit constituting the terminal portion. The branched polymer (A) includes a trivalent or higher valent structural unit constituting the branched portion and a monovalent structural unit constituting the terminal portion, and may include a divalent structural unit. The polymer (A) may contain only one type of each structural unit, or may contain a plurality of types of each. In the polymer (A), the structural units are bonded to each other at "monovalent" to "trivalent or higher" binding sites. Hereinafter, the monovalent structural unit may be referred to as “structural unit T”, the divalent structural unit may be referred to as “structural unit L”, and the trivalent or higher structural unit may be referred to as “structural unit B”.

(Structural unit including aromatic amine structure)
The structural unit containing the aromatic amine structure is a monovalent or higher structural unit, and is preferably a divalent or higher structural unit from the viewpoint of obtaining excellent charge transportability. From the same viewpoint, it is preferably a hexavalent or lower structural unit, and more preferably a tetravalent or lower structural unit. The structural unit containing the aromatic amine structure does not contain an alkyl group having 5 or more carbon atoms from the viewpoint of improving the characteristics of the organic electronic device.

As the aromatic amine structure, a tertiary aromatic amine structure is preferable, and a triarylamine structure (tertiary aromatic hydrocarbon structure) is more preferable. The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 6. The triphenylamine structure is particularly preferable from the viewpoint of obtaining excellent charge transportability.

The aromatic amine structure may be unsubstituted or the substituent may be attached to the aromatic amine structure. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms from the viewpoint of improving the solubility of the polymer (A). From the viewpoint of improving the solubility of the polymer (A), the number of carbon atoms is preferably 2 to 4, more preferably 3 or 4, and even more preferably 4.

Further, from the viewpoint of improving the device characteristics, an alkyl group having 5 or more carbon atoms is not bonded to the aromatic amine structure. "The alkyl group having 5 or more carbon atoms is not bonded to the aromatic amine structure" means that there is an alkyl group having 5 or more carbon atoms that is directly bonded to the aromatic ring and N (nitrogen atom) constituting the aromatic amine structure. It means that there is no alkyl group having 5 or more carbon atoms bonded to the aromatic ring and N (nitrogen atom) constituting the aromatic amine structure via an arbitrary atom or atomic group. Examples of the arbitrary atom or atomic group include "-O-" (ether bond), "-C (= O)-" (carbonyl bond) and the like.

Examples of the structural unit containing the aromatic amine structure include the following.
<< Divalent structural unit including aromatic amine structure >>

In the formula, R independently represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The number of carbon atoms is preferably 2 to 4, more preferably 3 to 4, and particularly preferably 4. In a preferred example, each structural unit has at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. In a more preferable example, in each structural unit, one of R is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the remaining R is a hydrogen atom.

<< Structural unit of trivalent or higher including aromatic amine structure >>

In the formula, Ar independently represents an arylene group or a heteroarylene group. It is preferably an arylene group. The arylene group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 6. The arylene group is preferably a phenylene group. Ar may have a substituent, and an example of the substituent is the same as R in the divalent structural unit containing the aromatic amine structure described above. In one example, all of Ar in each structural unit are unsubstituted. Y represents a divalent linking group, and examples thereof include a divalent group obtained by removing one hydrogen atom from a group having one or more hydrogen atoms in R in the structural unit l described later. Y also does not contain an alkyl group having 5 or more carbon atoms.

<< Monovalent structural unit including aromatic amine structure >>

In the formula, R is the same as R in the divalent structural unit including the above-mentioned aromatic amine structure. In one example, in each structural unit, all of R are hydrogen atoms.

The structural unit containing an aromatic amine structure is not limited as long as it contains an aromatic amine structure and does not contain an alkyl group having 5 or more carbon atoms.

(Structural unit including carbazole structure)
The structural unit containing the carbazole structure is a monovalent or higher structural unit, and is preferably a divalent or higher structural unit from the viewpoint of obtaining excellent charge transportability. From the same viewpoint, it is preferably a hexavalent or lower structural unit, and more preferably a tetravalent or lower structural unit. The structural unit containing a carbazole structure does not contain an alkyl group having 5 or more carbon atoms from the viewpoint of improving the characteristics of the organic electronic device.

The carbazole structure may be unsubstituted or a substituent may be attached to the carbazole structure. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms from the viewpoint of improving the solubility of the polymer (A). From the viewpoint of improving the solubility of the polymer (A), the number of carbon atoms is preferably 2 to 4, more preferably 3 or 4, and even more preferably 4.

Further, from the viewpoint of improving the device characteristics, an alkyl group having 5 or more carbon atoms is not bonded to the carbazole structure. "No alkyl group having 5 or more carbon atoms is bonded to the carbazole structure" means that there is no alkyl group having 5 or more carbon atoms directly bonded to the benzene ring and N (nitrogen atom) constituting the carbazole structure. , Means that there is no alkyl group having 5 or more carbon atoms bonded to the benzene ring and N (nitrogen atom) constituting the carbazole structure via an arbitrary atom or atomic group. Examples of any atom or group of atoms are as described above.

Examples of the structural unit containing the carbazole structure include the following.
<< Divalent structural unit including carbazole structure >>

In the formula, R is the same as R in the divalent structural unit including the above-mentioned aromatic amine structure. Ar independently represents an aryl group or a heteroaryl group, or an arylene group or a heteroarylene group. It is preferably an aryl group or an arylene group. The aryl group and the arylene group preferably have 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms, and further preferably 6 carbon atoms. The aryl group is preferably a phenyl group, and the arylene group is preferably a phenylene group. Ar may have a substituent, and an example of the substituent is the same as R above. In a preferred example, each structural unit has at least one group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. In a more preferable example, in each structural unit, one of R is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, the remaining R is a hydrogen atom, and Ar optionally contained is not. Is it a substitution; or Ar has one R, the R being an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and the remaining R being a hydrogen atom.

<< Structural unit of trivalent or higher including carbazole structure >>

In the formula, Ar is independently the same as Ar in the trivalent or higher structural unit including the above-mentioned aromatic amine structure. The benzene ring and Ar may have a substituent, and an example of the substituent is the same as R in the divalent structural unit containing the aromatic amine structure described above. In one example, in each structural unit, the benzene ring and any Ar contained optionally are all unsubstituted. Y is the same as Y in the trivalent or higher structural unit including the above-mentioned aromatic amine structure.

<< Monovalent structural unit including carbazole structure >>

In the formula, R and Ar are the same as R and Ar in the divalent structural unit including the above-mentioned carbazole structure. In one example, in each structural unit, all of R are hydrogen atoms, and Ar optionally contained is unsubstituted.

The structural unit containing a carbazole structure is not limited as long as it contains a carbazole structure and does not contain an alkyl group having 5 or more carbon atoms.

(Structural unit containing thienyl group)
The polymer (A) has at least a structural unit containing a thienyl group which may have a substituent as a monovalent structural unit located at the end of the polymer chain. The structural unit containing a thienyl group does not contain an alkyl group having 5 or more carbon atoms from the viewpoint of improving the characteristics of the organic electronic device.

The thienyl group may be unsubstituted or may have a substituent. As the substituent, an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable, from the viewpoint of changing the solubility and solubility of the polymer (A). Is an alkyl group having 1 or 2 carbon atoms, particularly preferably a methyl group.

Further, the substituent which the thienyl group may have does not include an alkyl group having 5 or more carbon atoms from the viewpoint of improving the device characteristics. That is, an alkyl group having 5 or more carbon atoms is not bonded to the thienyl group directly or via an arbitrary atom or atomic group. Examples of any atom or group of atoms are as described above.

Examples of the thienyl group which may have a substituent include a 2-thienyl group and a 3-thienyl group which may have a substituent. The thienyl group is represented by, for example, the following formula (Ia) or formula (Ib).

（式（Ｉａ）及び（Ｉｂ）中のＲ^１〜Ｒ^３は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ^１〜Ｒ^３の少なくとも２つは水素原子である。）
アルキル基の炭素数は、好ましくは１〜３、より好ましくは１又は２、更に好ましくは１である。《Thienil group》

^{(R 1 to} R ³ in the formulas (Ia) and (Ib) independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least two of ^{R 1 to} R ^{3 are hydrogen atoms.} .)
The number of carbon atoms of the alkyl group is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

Examples of the structural unit containing a thienyl group include structural units represented by the following formulas (IIa) to (IIb-2).

（式（IIａ）及び（IIｂ）中のＲ^１〜Ｒ^３は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ^１〜Ｒ^３の少なくとも２つは水素原子であり、Ａｒは、アリーレン基又はヘテロアリーレン基を表し、ｎは、０又は１を表す。）<< Structural unit containing thienyl group >>

^{(R 1 to} R ³ in the formulas (IIa) and (IIb) independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least two of ^{R 1 to} R ^{3 are hydrogen atoms.} , Ar represents an arylene group or a heteroarylene group, and n represents 0 or 1).

（式（IIａ−１）及び（IIｂ−１）中のＲ及びＲ^１〜Ｒ^３は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ^１〜Ｒ^３の少なくとも２つは水素原子であり、Ａｒは、アリーレン基又はヘテロアリーレン基を表し、ｎは、０又は１を表す。）

^{(R and R 1 to} R ³ in the formulas (IIa-1) and (IIb-1) independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least 2 of ^{R 1 to} R ^{3 are represented.} One is a hydrogen atom, Ar represents an arylene group or a heteroarylene group, and n represents 0 or 1).

（式（IIａ−２）及び（IIｂ−２）中のＲ及びＲ^１〜Ｒ^３は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ^１〜Ｒ^３の少なくとも２つは水素原子であり、Ａｒは、アリーレン又はヘテロアリーレン基を表し、ｎは、０又は１を表す。）

^{(R and R 1 to} R ³ in the formulas (IIa-2) and (IIb-2) independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least 2 of ^{R 1 to} R ^{3 are represented.} One is a hydrogen atom, Ar represents an arylene or heteroarylene group, and n represents 0 or 1).

Specific examples of structural units containing a thienyl group are listed below. In the formula, n is 1 to 4.
《Thienil basal》

Among the above, the following structures are preferable from the viewpoints of increasing the change in solubility, reducing the influence of the hole transport site on the energy level, and improving productivity. In the formula, n is 1 to 4.

In the example of the structural unit containing a thienyl group and the example of the thienyl group group, the number of carbon atoms of the alkyl group is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

The polymer (A) has one or more terminal structural units containing a thienyl group which may have a substituent. When the polymer (A) has a branched structure, the end may be the end of the main chain or the end of the side chain, or may be the end of both the main chain and the side chain. Further, the polymer (A) may have a structural unit containing a thienyl group at all the terminals, or may have a structural unit at a part of all the terminals. Specifically, when the polymer (A) has two ends and has a structural unit containing a thienyl group at the two ends, the polymer (A) has three or more ends and the three or more ends. When it has a structural unit containing a thienyl group at three or more of the terminals of the above, and the like.

Further, the polymer (A) preferably has a structural unit containing a thienyl group at all the ends from the viewpoint of increasing the change in the solubility of the composition, and has three or more ends. It is more preferable that all of them have a structural unit containing a thienyl group. The fact that the polymer (A) has three or more ends, that is, that it has a branched structure, can increase the weight average molecular weight, increase the glass transition temperature, and contribute to the improvement of heat resistance. It is also preferable from the viewpoint of.

(structure)
Examples of the partial structure contained in the polymer (A) include the following. The polymer (A) is not limited to having the following partial structure. In the partial structure, "L" represents a divalent structural unit L, "B" represents a trivalent or higher structural unit B, and "T" represents a monovalent structural unit T. "*" Represents a binding site with another structural unit. The structural units L, B and T do not contain an alkyl group having 5 or more carbon atoms in each structural unit.

Linear polymer (A)

Branched polymer (A)

In the polymer (A), preferably, the structural unit L and / or the structural unit B contains at least one selected from the group consisting of a structural unit containing an aromatic amine structure and a structural unit containing a carbazole structure, and more preferably. Contains at least one selected from the group consisting of a structural unit containing an aromatic amine structure and a structural unit containing a carbazole structure in both the structural unit L and the structural unit B. Further, the structural unit T contains at least a structural unit containing a thienyl group which may have a substituent, and is selected from the group consisting of a structural unit containing an aromatic amine structure and a structural unit containing a carbazole structure. It may contain seeds. The plurality of structural units L may be the same structural unit or different structural units from each other. The same applies to the structural unit T and the structural unit B.

(Arbitrary structural unit)
The structural unit L may include any divalent structural unit l other than the structural unit containing an aromatic amine structure and the structural unit containing a carbazole structure. The structural unit B may include any trivalent or higher structural unit b other than the structural unit containing an aromatic amine structure and the structural unit containing a carbazole structure. The structural unit T may include any monovalent structural unit t other than the structural unit containing a thienyl group, the structural unit containing an aromatic amine structure, and the structural unit containing a carbazole structure. Any structural unit also does not contain an alkyl group having 5 or more carbon atoms in the structural unit.

(Structural unit l)
The structural unit l is a divalent structural unit having charge transportability. The structural unit l is not particularly limited as long as it includes an atomic group capable of transporting electric charges. For example, the structural unit l is a substituted or unsubstituted thiophene structure, fluorene structure, benzene structure, biphenyl structure, terphenyl structure, naphthalene structure, anthracene structure, tetracene structure, phenanthrene structure, dihydrophenanthrene structure, pyridine structure, pyrazine structure. , Kinolin structure, isoquinoline structure, quinoxalin structure, aclysine structure, diazaphenanthrene structure, furan structure, pyrrole structure, oxazole structure, oxazole structure, thiazole structure, thiazazole structure, triazole structure, benzothiophene structure, benzoxazole structure, benzo It is selected from an oxazole structure, a benzothiazole structure, a benzothiazole structure, a benzotriazole structure, and a structure containing one or more of these.

Specific examples of the structural unit l include the following. The structural unit l is not limited to the following.

R independently represents a hydrogen atom or a substituent. Preferably, R is independently selected from the group consisting of ^{-R 1} , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ^{8, and halogen atoms.} R ^{1 to} R ⁸ independently represent a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 4 carbon atoms; or an aryl group or a heteroaryl group having 2 to 30 carbon atoms. The alkyl group may be further substituted with an aryl group or a heteroaryl group having 2 to 20 carbon atoms, and the aryl group or the heteroaryl group may be further substituted with a linear, cyclic or branched group having 1 to 4 carbon atoms. It may be substituted with an alkyl group. R is preferably a hydrogen atom, an alkyl group, an aryl group, and an alkyl-substituted aryl group.

(Structural unit b)
The structural unit b is a trivalent or higher structural unit constituting the branched portion when the polymer (A) has a branched structure. The structural unit b is preferably hexavalent or less, and more preferably trivalent or tetravalent, from the viewpoint of improving the durability of the organic electronic device. The structural unit b is preferably a unit having charge transportability. For example, the structural unit b is preferably selected from a substituted or unsubstituted condensed polycyclic aromatic hydrocarbon structure from the viewpoint of improving the durability of the organic electronic device.

Specific examples of the structural unit b include the following. The structural unit b is not limited to the following.

W represents a trivalent linking group, for example, an arene triyl group having 2 to 30 carbon atoms or a heteroarene triyl group. Ar independently represents a divalent linking group, and for example, each independently represents an arylene group or a heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group. Z represents either a carbon atom, a silicon atom, or a phosphorus atom. In the structural unit, the benzene ring and Ar may have a substituent, and examples of the substituent include R in the structural unit l.

(Structural unit t)
The structural unit t is a monovalent structural unit constituting the terminal portion of the polymer (A). The structural unit t is not particularly limited, and includes, for example, a substituted or unsubstituted aromatic hydrocarbon structure, an aromatic heterocyclic structure (excluding the thienyl group), and one or more of these. Selected from the structure. In one embodiment, the structural unit t is preferably a substituted or unsubstituted aromatic hydrocarbon structure from the viewpoint of imparting durability without reducing charge transportability, and is preferably a substituted or unsubstituted benzene. The structure is more preferable.

Specific examples of the structural unit t include the following. The structural unit t is not limited to the following.

R is the same as R in the structural unit l.

In the above description of the structural unit, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle. An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle. The arenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. A heteroarene triyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic heterocycle. Examples of the aromatic hydrocarbon include a monocyclic ring, a condensed ring, and a polycycle in which two or more selected from a monocyclic ring and a condensed ring are bonded via a single bond. Examples of the aromatic heterocycle include a monocyclic ring, a condensed ring, and a polycycle in which two or more selected from a monocyclic ring and a condensed ring are bonded via a single bond.

Examples of aromatic hydrocarbons include benzene, biphenyl, terphenyl, triphenylbenzene, naphthalene, anthracene, tetracene, fluorene and phenanthrene. Examples of the aromatic heterocycle include pyridine, pyrazine, quinoline, isoquinolin, aclysine, phenanthroline, furan, pyrrole, thiophene, carbazole, oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzoxadiazole, and benzothiazole. Examples thereof include benzotriazole and benzothiophene.

(Alkyl group in polymer (A))
The polymer (A) does not contain an alkyl group having 5 or more carbon atoms. In the polymer (A), the content of the alkyl group having 5 or more carbon atoms is 0 mol% based on all the structural units. Here, the "content of an alkyl group having 5 or more carbon atoms" refers to the ratio of structural units having an alkyl group having 5 or more carbon atoms. When the polymer (A) contains an alkyl group having 5 or more carbon atoms, the wettability of the organic layer formed by using the polymer (A) is lowered. As a result, it is considered that another organic layer (upper layer) cannot be satisfactorily formed on the organic layer (lower layer) by the coating method, and the characteristics of the organic electronic device are deteriorated.

Further, in the polymer (A), the content of the alkyl group having 1 to 4 carbon atoms is 30 mol based on the total structural unit from the viewpoint of improving the solubility of the polymer (A) and improving the characteristics of the organic electronic device. % Or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more. Further, the number of alkyl groups having 1 to 4 carbon atoms is preferably 90 mol% or less based on all structural units from the viewpoint of improving the characteristics of the organic electronic device and satisfactorily synthesizing the branched polymer. It is more preferably 80 mol% or less, and further preferably 70 mol% or less. Here, the "content of an alkyl group having 1 to 4 carbon atoms" refers to the ratio of structural units having an alkyl group having 1 to 4 carbon atoms.

When the polymer (A) contains an alkyl group having 1 to 4 carbon atoms, the solubility of the polymer (A) in the solvent is improved when the composition contains a solvent, and a homogeneous composition can be obtained. By using the composition, a good organic layer can be formed. As a result, it is considered that the characteristics of the organic electronic device are improved.

(Number average molecular weight)
The number average molecular weight of the polymer (A) can be appropriately adjusted in consideration of solubility in a solvent, film forming property, and the like. The number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more, from the viewpoint of excellent charge transportability. The number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, and more preferably 50,000 or less, from the viewpoint of maintaining good solubility in the solvent and facilitating the preparation of the ink composition. The following is more preferable.

(Weight average molecular weight)
The weight average molecular weight of the polymer (A) can be appropriately adjusted in consideration of solubility in a solvent, film forming property, and the like. The weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, from the viewpoint of excellent charge transportability. The weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, and more preferably 400,000 or less, from the viewpoint of maintaining good solubility in the solvent and facilitating the preparation of the ink composition. The following is more preferable.

The number average molecular weight and the weight average molecular weight can be measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

(Ratio of structural units)
When the polymer (A) contains the structural unit L, the ratio of the structural unit L is preferably 10 mol% or more, more preferably 20 mol% or more, based on all the structural units, from the viewpoint of obtaining sufficient charge transportability. , 30 mol% or more is more preferable. Further, the ratio of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, considering the structural unit T and the structural unit B to be introduced as needed.

The total ratio of the structural unit containing the aromatic amine structure and the structural unit containing the carbazole structure in the structural unit L is preferably 50 mol% or more based on the total structural unit L from the viewpoint of obtaining excellent charge transportability. 70 mol% or more is more preferable, and 90 mol% or more is further preferable. The upper limit can be 100 mol%.

When the polymer (A) contains the structural unit B, the ratio of the structural unit B is preferably 1 mol% or more, more preferably 5 mol% or more, based on all the structural units, from the viewpoint of improving the durability of the organic electronic device. It is preferable, and 10 mol% or more is more preferable. The ratio of the structural unit B is preferably 50 mol% or less, preferably 40 mol% or less, from the viewpoint of suppressing an increase in viscosity and satisfactorily synthesizing the polymer (A) or obtaining sufficient charge transportability. Is more preferable, and 30 mol% or less is further preferable.

The total ratio of the structural unit containing the aromatic amine structure and the structural unit containing the carbazole structure in the structural unit B is preferably 50 mol% or more based on the total structural unit B from the viewpoint of obtaining excellent charge transportability. 70 mol% or more is more preferable, and 90 mol% or more is further preferable. The upper limit can be 100 mol%.

The ratio of the structural unit T contained in the polymer (A) is based on all the structural units from the viewpoint of improving the characteristics of the organic electronic device or from the viewpoint of suppressing the increase in viscosity and satisfactorily synthesizing the polymer (A). 5 mol% or more is preferable, 10 mol% or more is more preferable, and 15 mol% or more is further preferable. The ratio of the structural unit T is preferably 60 mol% or less, more preferably 55 mol% or less, still more preferably 50 mol% or less, from the viewpoint of obtaining sufficient charge transportability.

The ratio of the structural unit containing the thienyl group in the structural unit T is preferably 20 mol% or more, more preferably 50 mol% or more, based on the total structural unit T, from the viewpoint of sufficiently changing the solubility of the composition. 70 mol% or more is more preferable. The upper limit can be 100 mol%.

Considering the balance of charge transportability, durability, productivity, etc., the ratio (molar ratio) of the structural unit L and the structural unit T is preferably L: T = 100: 1 to 70, more preferably 100: 3 to 50. It is preferable, and 100: 5 to 30 is more preferable. When the charge transporting polymer contains the structural unit B, the ratio (molar ratio) of the structural unit L, the structural unit T, and the structural unit B is L: T: B = 100: 10 to 200: 10 to 100. Preferably, 100: 20 to 180: 20 to 90 is more preferable, and 100: 40 to 160: 30 to 80 is even more preferable.

The proportion of alkyl groups having 5 or more carbon atoms, the proportion of alkyl groups having 1 to 4 carbon atoms, and the proportion of structural units are the amounts of monomers charged corresponding to each structural unit used for synthesizing the polymer (A). Can be obtained using. Further, the ratio of the structural units can be calculated as an average value by using the integrated value of the spectrum derived from each structural unit in ^{the 1 H NMR spectrum of the polymer (A).} Since it is simple, when the amount to be charged is clear, the value obtained by using the amount to be charged is preferably adopted.

(Surface free energy)
Polymer (A) preferably has a surface free energy expressed as the sum of two components of the polar component and a nonpolar component by Owens-We n dt method is 41 mJ / ^{m 2} or more. The surface free energy is more preferably 42 mJ / m ² or more. Due to the large surface free energy of the polymer (A), the wettability of the organic layer (lower layer) formed by using the polymer (A) is improved. As a result, a good organic layer (upper layer) can be formed on the organic layer (lower layer), and it is considered that the characteristics of the organic electronic device are improved.

Surface free energy, from the viewpoint of forming an excellent organic layer, it is preferably 50 mJ / ^{m 2} or less, more preferably 45 mJ / ^{m 2} or less.

The surface free energy of the polymer (A) defined in the present embodiment means the surface free energy of the polymer film formed by using the polymer (A). Surface free energy, the following equation (1), based on the Owens-We n dt method, a surface free energy expressed as the sum of two components of the polar component and a nonpolar component.

According to Young's equation, the relationship between the contact angle between liquid and solid and the surface free energy can be expressed by the following equation (2). Here, γ _S indicates the surface free energy of the solid, γ _L indicates the surface free energy _{of the liquid, γ LS} indicates the interface free energy of the liquid / solid, and θ indicates the contact angle.

Each surface free energy that decreases as a result of the contact of two substances, such as a liquid and a solid, can be expressed as the sum of the geometric mean of the corresponding surface free energies, as expressed by equation (3) below. Suppose. The subscripts p and d indicate that the respective surface free energies are polar components (p) or non-polar components (d).

_{By eliminating γ LS} from the above equations (2) and (3), the following equation (4) is obtained.

Therefore, the contact angle of a solvent having a known surface free energy can be measured, and the surface free energy of the polymer film can be calculated using the above formula (4). That is, two types of droplets of water and diiodomethane are dropped on the polymer film, and the contact angle of each is measured. Water has a polar component of 51.0 mJ / m ² and a non-polar component of 21.8 mJ / m ² , and diiodomethane has a polar component of 1.3 mJ / m ² and a non-polar component of 49.5 mJ / m ² . Therefore, the surface free energy (polar component, non-polar component) of the polymer film can be calculated by solving the simultaneous equations by inputting the two contact angles.

ただし、式（５）及び式（６）中、
γ_ＬｐＭ：ジヨードメタンの表面自由エネルギーの極性成分、
γ_ＬｄＭ：ジヨードメタンの表面自由エネルギーの非極性成分、
γ_ＬＭ：ジヨードメタンの表面自由エネルギー（＝γ_ＬｐＭ＋γ_ＬｄＭ）、
θ_Ｍ：ポリマー膜に対するジヨードメタンの接触角、
γ_ＬｐＷ：水の表面自由エネルギーの極性成分、
γ_ＬｄＷ：水の表面自由エネルギーの非極性成分、
γ_ＬＷ：水の表面自由エネルギー（＝γ_ＬｐＷ＋γ_ＬｄＷ）、
θ_Ｗ：ポリマー膜に対する水の接触角、
γ_ｓｐ：ポリマー膜の表面自由エネルギーの極性成分、
γ_ｓｄ：ポリマー膜の表面自由エネルギーの非極性成分、をそれぞれ表す。More specifically, the simultaneous equations are shown in the following equations (5) and (6).

However, in equations (5) and (6),
γ _LpM : Polar component of surface free energy of diiodomethane,
γ _LdM : Non-polar component of surface free energy of diiodomethane,
γ _LM : Surface free energy of diiodomethane (= γ _LpM + γ _LdM ),
θ _M : Diiodomethane contact angle with respect to polymer membrane,
γ _LpW : Polar component of surface free energy of water,
γ _LdW : Non-polar component of surface free energy of water,
γ _LW : Surface free energy of water (= γ _LpW + γ _LdW ),
θ _W : Water contact angle with respect to the polymer membrane,
γ _sp : Polar component of the surface free energy of the polymer film,
γ _sd : Represents a non-polar component of the surface free energy of the polymer film, respectively.

The contact angle with respect to the polymer film refers to the contact angle measured for forming a polymer film composed of the polymer (A) using a solution containing only the polymer (A) and a solvent. The method for measuring the contact angle of the polymer film can follow, for example, the method shown in the examples.

(Production method)
The polymer (A) can be produced by various synthetic methods and is not particularly limited. For example, it is possible to use Suzuki coupling, Negishi coupling, its head coupling, Stille coupling, a known coupling reaction such as Buchwald-Hartwig coupling. Suzuki coupling causes a Pd-catalyzed cross-coupling reaction between an aromatic boronic acid derivative and an aromatic halide. According to Suzuki Coupling, the polymer (A) can be easily produced by binding desired aromatic rings to each other.

In the coupling reaction, for example, a Pd (0) compound, a Pd (II) compound, a Ni compound and the like are used as the catalyst. Further, a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate or the like as a precursor and mixing with a phosphine ligand can also be used.

[Initiator (B)]
The initiator (B) is used to change the solubility of the composition. As the initiator (B), a substance that can act as an oxidizing agent in the composition can be used. It is preferable to use a substance that can act as an oxidizing agent for the polymer (A) from the viewpoint of improving hole transportability. As the initiator (B), an onium salt composed of a cation and an anion is preferable from the viewpoint of changing the solubility of the composition, and examples thereof will be described below.

[Cation]
Examples of cations include H ⁺ , carbenium ion, ammonium ion, anilinium ion, pyridinium ion, imidazolium ion, pyrrolidinium ion, quinolinium ion, immonium ion, aminium ion, oxonium ion, and pyrylium ion. , Chromenilium ion, xanthylium ion, iodonium ion, sulfonium ion, phosphonium ion, tropyrium ion, cation having transition metal, etc., carbenium ion, ammonium ion, anilinium ion, aminium ion, iodonium ion , Sulfonium ion, and tropylium ion are preferable. Ammonium ion, anilinium ion, iodonium ion, and sulfonium ion are more preferable from the viewpoint of compatibility between the change property of the solubility of the composition and the storage stability.

[Anion]
Examples of anions include halogen ions such as ^{F −} , Cl ⁻ , Br ⁻ , and I ^{− ; OH −} ; ClO ₄ ⁻ ; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ^−. , CF ₃ SO ₃ ⁻ and other sulfonic acid ions; HSO ₄ ⁻ , SO ₄ ^2- and other sulfate ions; HCO ₃ ⁻ , CO ₃ ^2- and other carbonate ions; H ₂ PO ₄ ⁻ , HPO ₄ ^{2 -,} phosphate ion such as _{^{PO 4 3-; PF 6 -,}} PF 5 OH - fluorophosphate ions such _{as; [(CF 3 CF 2)} 3 PF 3] -, [(CF 3 CF 2 CF 2 ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ and other fluorinated alkylfluorophosphate ions; (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ^−, etc. fluoroalkane methide, imide ion _{^{such; BF 4 -, B (C}} 6 F 5) 4 -, B (C 6 H 4 CF 3) 4 - borate ions such _{^{as; SbF 6 -, SbF 5 OH}} - , etc. fluoroantimonic acid ions _{^{such; AsF 6 -, AsF 5 OH}} - fluoroarsenate periodate ions such as; AlCl ₄ ^-, BiF ₆ ^-, and the like. From the viewpoint of the change characteristics of the solubility of the composition when used in combination with the above-mentioned cations, fluorophosphate ions such as _{PF 6} ⁻ and PF ₅ OH ⁻ _{; [(CF 3} CF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF _{3) 2 CF)} ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ and other fluorinated alkylfluorophosphate ions; (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃₎ SO ₂ ) Fluoroalcan sulfonylmethides, imide ions such as ₂ N ⁻ ; borate ions such as _{BF 4} ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , B (C ₆ H ₄ CF ₃ ) ₄ ^{−, and} , SbF ₆ ⁻ , SbF ₅ OH ⁻ and other fluoroantimonate ions are preferable, and borate ions are particularly preferable.

More specifically, one selected from ammonium ion, anilinium ion, iodonium ion, and sulfonium ion, fluorophosphate ions, fluorinated alkylfluorophosphate ions, fluoroalcansulfonylmethide, and imide ions. , Borate ions, and one selected from fluoroantimonate ions are preferred. More preferably, it is an initiator containing ammonium ions and borate ions. Specific examples of the anions and cations contained in these preferred initiators are not limited to the above, and known anions and cations can be used.

[Solvent (C)]
The composition may further contain a solvent. As the solvent, a solvent capable of forming a coating layer using the composition can be used, and preferably a solvent capable of dissolving the polymer (A) and the initiator (B) can be used.

Examples of the solvent include water; alcohols such as methanol, ethanol and isopropyl alcohol; alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetraline and diphenylmethane. Alibo ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol, 2-methoxytoluene, 3- Aromatic ethers such as methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate; phenyl acetate , Aromatic esters such as phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide; dimethylsulfoxide, Examples thereof include tetrahydrofuran, acetone, chloroform, methylene chloride and the like. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, and aromatic ethers.

[Other optional ingredients]
The composition may further contain a charge transporting small molecule compound, other polymers and the like.

[Content]
The composition may contain only one type of the polymer (A) or two or more types. The content of the polymer (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass, based on the mass of the composition (excluding the solvent) from the viewpoint of obtaining good charge transportability. More preferably by mass% or more. Further, in consideration of the content of the initiator (B), 99.99% by mass or less is preferable, 99.9% by mass or less is more preferable, and 99. More preferably, it is 5% by mass or less.

The composition may contain only one kind of initiator (B) or two or more kinds. The content of the initiator (B) is preferably 0.01% by mass or more, preferably 0.1% by mass or more, based on the mass of the composition (excluding the solvent) from the viewpoint of sufficiently changing the solubility. More preferably, 0.5% by mass or more is further preferable. Further, from the viewpoint of maintaining good film-forming property, 50% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is further preferable with respect to the mass of the composition (excluding the solvent).

The composition may contain only one type of solvent (C) or two or more types. The content of the solvent (C) can be determined in consideration of application to various coating methods. For example, the content of the solvent is preferably such that the ratio of the polymer (A) to the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass or more. Is more preferable. The content of the solvent is preferably such that the ratio of the polymer (A) to the solvent is 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

[Change in solubility]
The solubility of the composition can be changed by light irradiation and / or heating, so that the composition can be laminated by coating with the same solvent. For light irradiation, for example, light having a wavelength of 200 to 800 nm can be used. The heating temperature is preferably 60 to 300 ° C, more preferably 80 to 250 ° C, and even more preferably 100 to 220 ° C. The heating time is preferably 10 seconds to 2 hours, more preferably 1 minute to 1 hour, and even more preferably 1 to 10 minutes.

The mechanism by which the solubility of the composition changes is not clear, but in one example of the mechanism, thienyl groups form bonds, for example, thienyl groups form covalent bonds by light and / or heat and the action of the initiator. , It is estimated that the solubility of the composition changes. The polymer (A) may have a group forming a bond such as a carbon-carbon double bond group or a group having a small ring, but from the viewpoint of improving the device characteristics, the polymer (A) may have a bond other than the thienyl group. It is not necessary to have a group forming the above. Since the composition has a variable solubility, the composition can be used as a curable resin composition as an embodiment.

In order to make the organic layer multi-layered, it is preferable that the degree of change in the solubility of the composition in the solvent is large. "The solubility of the composition changes" can be confirmed by whether or not the solubility of the organic layer formed by using the composition in the solvent changes before and after applying light and / or heat. Specifically, first, an organic layer (1) is formed by a coating method using a composition containing a polymer or oligomer (A), an initiator (B), and a solvent (1). After undergoing an arbitrary drying step, light and / or heat is applied to the organic layer (1) to obtain the organic layer (2). Subsequently, the organic layer (2) is brought into contact with the solvent (2) to obtain the organic layer (3). It can be said that the larger the film thickness of the obtained organic layer (3), the greater the degree of change in the solubility of the composition. That is, it is preferable that the ratio of the film thickness of the organic layer (3) to the film thickness of the organic layer (2) (that is, the residual ratio of the organic layer) is large. The residual ratio can be determined by the ratio of the measured values of the film thickness of the organic layer (2) and the organic layer (3) or the ratio of the measured values of the absorbance of the organic layer (2) and the organic layer (3).

At this time, as the solvent (2), the same solvent as the solvent (1), and when the solvent (1) is a mixed solvent, the solvent having the largest weight ratio contained in the solvent (1) or toluene shall be used. Can be done. Confirmation using toluene is easy.

Since the composition of the present embodiment contains the polymer (A) having a structural unit containing an aromatic amine structure and / or a structural unit containing a carbazole structure, organic electronics such as an organic EL element and an organic photoelectric conversion element. It can be preferably used as a hole transport material composition used for forming an element.

<Hole transport material composition>
The hole transport material composition according to the embodiment of the present invention contains the composition of the embodiment. The hole transport material composition may contain the polymer (A) and the initiator (B). The hole transport material composition may further contain a small molecule compound, a substance that can act as a dopant, and the like.

<Ink composition>
The ink composition according to the embodiment of the present invention contains the composition of the embodiment. The ink composition may include the polymer (A) and the initiator (B), and generally a solvent capable of dissolving or dispersing them. By using the ink composition, the organic layer can be easily formed by a simple method such as a coating method.

<Organic layer and manufacturing method of organic layer>
The organic layer according to the embodiment of the present invention is formed by applying the composition, the hole transport material composition, or the ink composition of the above embodiment and applying heat, light, or both heat and light. There is. Further, the method for producing an organic layer according to an embodiment of the present invention is a step of applying the composition, hole transport material composition, or ink composition of the embodiment to form a coating layer, and the coating. The layer comprises applying heat, light, or both heat and light.

Known coating methods include, for example, an inkjet method, a casting method, a dipping method, a letterpress printing, a concave plate printing, an offset printing, a flat plate printing, a letterpress reversal offset printing, a screen printing, a printing method such as gravure printing, and a spin coating method. Method can be mentioned. The coating can usually be carried out in a temperature range of -20 to + 300 ° C., preferably 10 to 100 ° C., particularly preferably 15 to 50 ° C. After coating, the obtained coating layer is dried by a hot plate or an oven in a temperature range of usually 60 to 300 ° C., preferably 80 to 250 ° C., particularly preferably 100 to 220 ° C. to remove the solvent. You may. The drying time is usually 10 seconds to 2 hours, preferably 1 minute to 1 hour, and particularly preferably 1 to 10 minutes.

By applying heat, light, or both heat and light to the coating layer formed by coating, an organic layer having a solubility different from that before the addition can be obtained. Since the organic layer has low solubility in a solvent, another organic layer can be easily formed on the organic layer of the present embodiment by using a coating solution.

Light sources such as low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, fluorescent lamps, light-emitting diodes, and sunlight can be used for light irradiation, and heating can be performed on a hot plate or in an oven. Can be done within.

The thickness of the organic layer can be appropriately set depending on the application. From the viewpoint of improving the efficiency of charge transport, it is preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more. The thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, and further preferably 100 nm or less from the viewpoint of reducing the electric resistance.

<Organic electronics element>
The organic electronic device according to the embodiment of the present invention has at least the organic layer of the embodiment. Examples of the organic electronics element include an organic EL element, an organic photoelectric conversion element, an organic transistor and the like. The organic electronic device preferably has a structure in which an organic layer is arranged between at least a pair of electrodes.

[Organic EL element]
The organic EL device according to the embodiment of the present invention has at least the organic layer of the embodiment. The organic EL element usually includes a light emitting layer, an anode, a cathode, and a substrate, and if necessary, provides other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. I have. Each layer may be formed by a thin-film deposition method or a coating method. The organic EL device preferably has an organic layer as a light emitting layer or another functional layer, more preferably as a functional layer, and further preferably as at least one of a hole injection layer and a hole transport layer.

FIG. 1 is a schematic cross-sectional view showing an embodiment of an organic EL device. The organic EL element of FIG. 1 is an element having a multi-layer structure, and includes a substrate 8, an anode 2, a hole injection layer 3 composed of the organic layer of the above embodiment, a hole transport layer 6, a light emitting layer 1, and an electron transport layer 7. The electron injection layer 5 and the cathode 4 are provided in this order. Hereinafter, each layer will be described.

[Light emitting layer]
As the material used for the light emitting layer, a light emitting material such as a small molecule compound, a polymer, or a dendrimer can be used. Polymers are preferred because they are highly soluble in solvents and suitable for coating methods. Examples of the light emitting material include fluorescent materials, phosphorescent materials, thermal activated delayed fluorescent materials (TADF) and the like.

As the fluorescent material, perylene, coumarin, rubrene, Kinaku chloride emissions, stilbene, dye laser dyes, aluminum complex, low-molecular compounds such as derivatives thereof; polyfluorene, polyphenylene, polyphenylene vinylene, polyvinyl carbazole, fluorene over benzothiadiazole co Polymers, fluorene-triphenylamine copolymers, polymers such as derivatives thereof; and mixtures thereof.

As the phosphorescent material, a metal complex containing a metal such as Ir or Pt can be used. Examples of the Ir complex include FIr (pic) (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate) that emits blue light, and Ir (ppy) _{3 that emits green light.} (Factris (2-phenylpyridine) iridium), emits red light (btp) ₂ Ir (acac) (bis [2- (2'-benzo [4,5-α] thienyl) pyridinate-N, C ³ ] Examples thereof include iridium (acetyl-acetonate)) and Ir (piq) ₃ (tris (1-phenylisoquinolin) iridium). Examples of the Pt complex include PtOEP (2 , 3 , 7 , 8 , 12 , 13 , 13, 17 , 18-octaethyl-21H , 23H-forfin platinum) that emits red light.

When the light emitting layer contains a phosphorescent material, it is preferable that the light emitting layer further contains a host material in addition to the phosphorescent material. Small molecule compounds, polymers, or dendrimers can be used as the host material. Examples of low molecular weight compounds include CBP (4,4'-bis (9H-carbazole-9-yl) biphenyl), mCP (1,3-bis (9-carbazolyl) benzene), and CDBP (4,4'-. Bis (carbazole-9-yl) -2,2'-dimethylbiphenyl), derivatives thereof and the like, examples of the polymer include the composition of the above embodiment, polyvinylcarbazole, polyphenylene, polyfluorene, derivatives thereof and the like. ..

Examples of thermally activated delayed fluorescent materials include Adv. Mater., 21, 4802-4906 (2009); Appl. Phys. Lett., 98, 083302 (2011); Chem. Comm., 48, 9580 (2012). Appl. Phys. Lett., 101, 093306 (2012); J. Am. Chem. Soc., 134, 14706 (2012); Chem. Comm., 48, 11392 (2012); Nature, 492, 234 (2012) ); Adv. Mater., 25, 3319 (2013); J. Phys. Chem. A, 117, 5607 (2013); Phys. Chem. Chem. Phys., 15, 15850 (2013); Chem. Comm., 49, 10385 (2013); Chem. Lett., 43, 319 (2014) and the like.

[Hole injection layer, hole transport layer]
The organic layer formed by using the above composition is preferably used as at least one of the hole injection layer and the hole transport layer, and more preferably at least as the hole injection layer. When the organic EL device has an organic layer formed by using the above composition as a hole injection layer and further has a hole transport layer, a known material can be used for the hole transport layer. Further, when the organic EL device has an organic layer formed by using the above composition as a hole transport layer and further has a hole injection layer, a known material can be used for the hole injection layer. Further, the organic EL element may have an organic layer as a hole injection transport layer or two organic layers as a hole injection layer and a hole transport layer.

[Electron transport layer, electron injection layer]
Materials used for the electron transport layer and the electron injection layer include, for example, fused ring tetracarboxylic acid anhydrides such as phenanthroline derivative, bipyridine derivative, nitro-substituted fluorene derivative, diphenylquinone derivative, thiopyrandioxide derivative, naphthalene and perylene, and carbodiimide. , Fluolenilidene methane derivative, anthraquinodimethane and antron derivative, oxadiazole derivative, thiadiazole derivative, benzoimidazole derivative, quinoxalin derivative, aluminum complex and the like. Moreover, the composition of the said embodiment can also be used.

[cathode]
As the cathode material, for example, a metal or a metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg / Ag, LiF, CsF is used.

[anode]
As the anode material, for example, a metal (for example, Au) or another conductive material is used. Other materials include, for example, oxides (eg, ITO: indium oxide / tin oxide), conductive polymers (eg, polythiophene-polystyrene sulfonic acid mixture (PEDOT: PSS)).

[substrate]
As the substrate, glass, plastic, etc. can be used. The substrate is preferably transparent and preferably has flexibility. Quartz glass, light-transmitting resin film and the like are preferably used.

Examples of the resin film include films made of polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyetherimide, polyetherether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate and the like. Can be mentioned.

When a resin film is used, the resin film may be coated with an inorganic substance such as silicon oxide or silicon nitride in order to suppress the permeation of water vapor, oxygen and the like.

[Emission color]
The emission color of the organic EL element is not particularly limited. The white organic EL element is preferable because it can be used for various lighting fixtures such as household lighting, vehicle interior lighting, clocks, and liquid crystal backlights.

As a method for forming a white organic EL element, a method can be used in which a plurality of luminescent materials are used to simultaneously emit a plurality of luminescent colors to mix the colors. The combination of a plurality of emission colors is not particularly limited, but is a combination containing three emission maximum wavelengths of blue, green and red, a combination containing two emission maximum wavelengths such as blue and yellow, yellowish green and orange, and the like. Can be mentioned. The emission color can be controlled by adjusting the type and amount of the emission material.

<Display element, lighting device, display device>
The display element according to the embodiment of the present invention includes the organic EL element according to the embodiment. For example, by using an organic EL element as an element corresponding to each pixel of red, green, and blue (RGB), a color display element can be obtained. There are two methods for forming an image: a simple matrix type in which individual organic EL elements arranged on a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which a thin film transistor is arranged and driven in each element.

Further, the lighting device according to the embodiment of the present invention includes the organic EL element according to the embodiment of the present invention. Further, the display device according to the embodiment of the present invention includes a lighting device and a liquid crystal element as a display means. For example, the display device can be a display device using a lighting device according to an embodiment of the present invention as a backlight and a known liquid crystal element as a display means, that is, a liquid crystal display device.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Synthesis of hole-transporting polymer]
<Preparation of Pd catalyst>
Tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) was weighed in a sample tube at room temperature in a glove box under a nitrogen atmosphere, toluene (15 mL) was added, and the mixture was stirred for 30 minutes. Similarly, tris (t-butyl) phosphine (129.6 mg, 640 μmol) was weighed into a sample tube, toluene (5 mL) was added, and the mixture was stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes to prepare a catalyst. All solvents were used after being degassed by nitrogen bubbles for 30 minutes or longer.

<Synthesis of hole-transporting polymer 1>
In a three-necked round-bottom flask, monomer A1 (2.0 mmol), monomer B1 (5.0 mmol), monomer C1 (4.0 mmol), methyltri-n-octylammonium chloride (Alfa Aesar "Alicoat 336") (0.03 g). ), Potassium hydroxide (1.12 g), pure water (5.54 mL), and toluene (50 mL) were added, and the prepared Pd-catalyzed toluene solution (3.0 mL) was added. All solvents were used after being degassed by nitrogen bubbles for 30 minutes or longer. The mixture was heated to reflux for 2 hours. All operations up to this point were performed under a nitrogen stream.

After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9: 1). The resulting precipitate was collected by suction filtration and washed with methanol. The resulting precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate is collected by suction filtration, dissolved in toluene, and a metal adsorbent (“Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer” manufactured by Strem Chemicals, 200 mg per 100 mg of precipitate) is added. It was stirred in the evening. After the stirring was completed, the metal adsorbent and the insoluble matter were filtered off, and the filtrate was concentrated with a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol. The resulting precipitate was collected by suction filtration and washed with methanol. The obtained precipitate was vacuum dried to obtain a hole transporting polymer 1. The molecular weight was measured by GPC (polystyrene conversion) using THF as an eluent. The obtained hole-transporting polymer 1 had a number average molecular weight of 12,000 and a weight average molecular weight of 64,500.

The measurement conditions for the number average molecular weight and the weight average molecular weight are as follows.
Equipment: High Performance Liquid Chromatograph Prominence Shimadzu Corporation
Liquid transfer pump (LC-20AD)
Degassing unit (DGU-20A)
Autosampler (SIL-20AHT)
Column oven (CTO-20A)
PDA detector (SPD-M20A)
Differential Refractometer Detector (RID-20A)
Column: Gelpack®
GL-A160S (serial number: 686-1J27)
GL-A150S (serial number: 685-1J27) Hitachi Kasei Co., Ltd.
Eluent: Tetrahydrofuran (THF) (for HPLC, containing stabilizer) Wako Pure Chemical Industries, Ltd.
Flow velocity: 1 mL / min
Column temperature: 40 ° C
Detection wavelength: 254 nm
Molecular weight standard substance: PStQuick A / B / C Tosoh Corporation

<Synthesis of hole-transporting polymer 2>
Hole transportability Similar to the synthesis of the hole transport polymer 1, except that the monomers used are monomer A2 (2.0 mmol), monomer B1 (5.0 mmol), and monomer C1 (4.0 mmol). Polymer 2 was synthesized. The obtained hole-transporting polymer 2 had a number average molecular weight of 13,300 and a weight average molecular weight of 78,900.

<Synthesis of hole-transporting polymer 3>
Hole transportability Similar to the synthesis of the hole transport polymer 1 except that the monomers used are monomer A1 (2.0 mmol), monomer B1 (5.0 mmol), and monomer C2 (4.0 mmol). Polymer 3 was synthesized. The obtained hole-transporting polymer 3 had a number average molecular weight of 12,500 and a weight average molecular weight of 47,100.

<Synthesis of hole-transporting polymer 4>
Hole transportability Similar to the synthesis of the hole transport polymer 1, except that the monomers used are monomer A1 (2.0 mmol), monomer B1 (5.0 mmol), and monomer C3 (4.0 mmol). Polymer 4 was synthesized. The obtained hole-transporting polymer 4 had a number average molecular weight of 11,800 and a weight average molecular weight of 63,100.

<Synthesis of hole-transporting polymer 5>
Hole transportability Similar to the synthesis of the hole transport polymer 1 except that the monomers used are monomer A1 (2.0 mmol), monomer B1 (5.0 mmol), and monomer C4 (4.0 mmol). Polymer 5 was synthesized. The obtained hole-transporting polymer 5 had a number average molecular weight of 9,800 and a weight average molecular weight of 52,100.

<Synthesis of hole-transporting polymer 6>
Hole transportability Similar to the synthesis of the hole transport polymer 1, except that the monomers used are monomer A2 (2.0 mmol), monomer B1 (5.0 mmol), and monomer C3 (4.0 mmol). Polymer 6 was synthesized. The obtained hole-transporting polymer 6 had a number average molecular weight of 10,000 and a weight average molecular weight of 56,000.

<Synthesis of hole-transporting polymer 7>
Hole transportability Similar to the synthesis of the hole transport polymer 1, except that the monomers used are monomer A1 (2.0 mmol), monomer B2 (5.0 mmol), and monomer C3 (4.0 mmol). Polymer 7 was synthesized. The obtained hole-transporting polymer 7 had a number average molecular weight of 11,100 and a weight average molecular weight of 68,000.

<Synthesis of hole-transporting polymer 8>
Synthesis of hole-transporting polymer 1 except that the monomers used are monomer A1 (2.0 mmol), monomer B1 (5.0 mmol), monomer C3 (1.0 mmol), and monomer T1 (3.0 mmol). In the same manner, the hole transporting polymer 8 was synthesized. The obtained hole-transporting polymer 8 had a number average molecular weight of 10,900 and a weight average molecular weight of 73,500.

<Synthesis of hole-transporting polymer 9>
Hole transportability Similar to the synthesis of the hole transport polymer 1, except that the monomers used are monomer A1 (2.0 mmol), monomer B1 (5.0 mmol), and monomer T2 (4.0 mmol). Polymer 9 was synthesized. The obtained hole-transporting polymer 9 had a number average molecular weight of 15,900 and a weight average molecular weight of 67,500.

The monomers used in the hole-transporting polymers 1-9 are summarized in Table 1 below.

The structural formula of the monomer is shown below.

[Examples 1 to 6 and Comparative Examples 1 and 2]
<Preparation and evaluation of solvent-resistant thin film (organic layer)>
The hole-transporting polymers 1 to 8 are each dissolved in toluene (polymer 4.5 mg / toluene 465 μL), and a toluene solution of the following initiator 1 or 2 (50 μL, initiator concentration 10 μg / 1 μL) is added to prepare an ink composition. Made. Further, in the same manner, an ink composition containing no initiator was also prepared. Both ink compositions were obtained as a uniform solution.

The prepared ink composition was spin-coated on a quartz glass plate having a size of 22 mm × 29 mm × thickness of 1 mm at room temperature (25 ° C.) at a rotation speed of 3,000 min ^-1 to form a thin film (1). Then, the thin film (1) was heated on a hot plate at 210 ° C. for 10 minutes to cure, and the thin film (2) (50 nm) was formed. The thin film (2) is grasped with tweezers together with the quartz glass plate, immersed in a 200 mL beaker filled with toluene (25 ° C.), and rinsed by vibrating 10 times in the thickness direction of the quartz glass plate for 10 seconds to rinse the thin film (2). 3) was obtained. The residual ratio (residual film ratio) of the thin film (3) was determined from the ratio of the absorbances of the thin films before and after rinsing. The results are summarized in Table 2.

The measurement conditions for absorbance are as follows.
The absorbance was measured using a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.). For the thin film, the absorbance at maximum absorption at 300 to 420 nm was determined.

As is clear from Table 2, all of the thin films (organic layers) obtained by using the ink composition according to the embodiment of the present invention showed excellent results with a residual ratio of 90% or more. The thin film (organic layer) obtained from the composition whose solubility changes has solvent resistance even when the polymer contained in the composition does not contain a general polymerizable substituent such as a styryl group or an oxetane group. Had had. From these examples, the effect of the thienyl group could be confirmed. By using a composition having a variable solubility, it is possible to form multiple layers by a coating method of an organic electronic device.

[Examples 7 to 12 and Comparative Examples 3 and 4]
<Evaluation of surface free energy>
The surface free energy was evaluated using the hole transporting polymers 1-8.
A toluene solution prepared by dissolving 10 mg of the polymer in 2 g of toluene was added dropwise onto a quartz glass substrate, and spin coating was performed under the conditions of ^{a rotation speed of 3,000 min -1 for 60 seconds.} Then, it was baked at 210 ° C. for 10 minutes to prepare a polymer film.

Pure water and diiodomethane were added dropwise to the polymer membrane, and the contact angles of each were measured by the following methods. A contact angle meter (“DropMaster500” manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement.

At room temperature (25 ° C.) in the air, 1 μL of pure water (25 ° C.) or diiodomethane (25 ° C.) was dispensed from the needle tip of a syringe (“DropMaster 500” standard accessory) to form droplets on the needle tip. The needle tip was brought close to the polymer membrane until the droplet touched the polymer membrane. The syringe was separated from the polymer membrane when the droplet touched the polymer membrane. The droplets 10 seconds after the droplets were deposited (after the droplets touched the polymer film) were image-analyzed, the contact angle was obtained by the θ / 2 method, and the average value of 4 times was calculated.

By substituting the contact angle (average value) into the above formulas (5) and (6), the polar component (mJ / m ² ) and the non-polar component (mJ / m ² ) of the surface free energy of the polymer film were calculated. The results are shown in Table 3.

As shown in Table 3, the surface free energy differs depending on the alkyl group contained in the polymer (A). The polymers of Comparative Examples 1 and 2 having an alkyl group having 5 or more carbon atoms have a low surface free energy, whereas the polymers of Examples 1 to 6 having no alkyl group having 5 or more carbon atoms have a low surface free energy. However, the results were as high as 41 mJ / m ^{2 or more.} In order to improve the wettability of the ink composition used for forming the upper hole transport layer, light emitting layer and the like, it is desirable that the surface free energy of the polymer (A) is high. Since the polymer (A) does not have an alkyl group having 5 or more carbon atoms, the film forming property of the upper layer is improved.

<Manufacturing of organic EL element>
An organic EL device containing any of the hole transporting polymers 1 to 8 in the hole injection layer was prepared, and the characteristics were evaluated.

[Example 7]
(Formation of hole injection layer)
An ink composition was prepared by mixing the hole-transporting polymer 3 (10.0 mg), the initiator 1 (0.5 mg), and toluene (2.3 mL) in an air atmosphere. The ink composition was spin-coated on a glass substrate in which ITO was patterned to a width of 1.6 mm at a rotation speed of 3,000 min ^-1 , and then heated on a hot plate at 200 ° C. for 30 minutes to be cured and a hole injection layer (a hole injection layer). 30 nm) was formed.

(Formation of hole transport layer)
An ink composition was prepared by mixing a hole-transporting polymer 9 (10.0 mg), an onium salt (the initiator 1) (0.5 mg), and toluene (2.3 mL) in an air atmosphere. The ink composition was spin-coated on the hole injection layer at a rotation speed of 3,000 min ^-1 , and then heated on a hot plate at 230 ° C. for 30 minutes in a nitrogen atmosphere to form a hole transport layer (30 nm). bottom.

The glass substrate was transferred into a vacuum vapor deposition machine, and on the hole transport layer, CBP: Ir (ppy) ₃ (94: 6, 30 nm), BAlq (10 nm), TPBi (30 nm), LiF (0.8 nm), And Al (100 nm) were deposited in this order by a vapor deposition method. Then, a sealing process was performed to produce an organic EL element.

[Example 8]
In the step of forming the hole injection layer in the organic EL device of Example 7, the organic EL device was produced in the same manner as in Example 7 except that the hole transporting polymer 3 was changed to the hole transporting polymer 4.

[Example 9]
In the step of forming the hole injection layer in the organic EL device of Example 7, the organic EL device was produced in the same manner as in Example 7 except that the hole transporting polymer 3 was changed to the hole transporting polymer 5.

[Example 10]
In the step of forming the hole injection layer in the organic EL device of Example 7, the organic EL device was produced in the same manner as in Example 7 except that the hole transporting polymer 3 was changed to the hole transporting polymer 6.

[Example 11]
In the step of forming the hole injection layer in the organic EL device of Example 7, the organic EL device was produced in the same manner as in Example 7 except that the hole transporting polymer 3 was changed to the hole transporting polymer 7.

[Example 12]
In the step of forming the hole injection layer in the organic EL device of Example 7, the organic EL device was produced in the same manner as in Example 7 except that the hole transporting polymer 3 was changed to the hole transporting polymer 8.

[Comparative Example 3]
In the step of forming the hole injection layer in the organic EL device of Example 7, the organic EL device was produced in the same manner as in Example 7 except that the hole transporting polymer 3 was changed to the hole transporting polymer 1.

[Comparative Example 4]
In the step of forming the hole injection layer in the organic EL device of Example 7, the organic EL device was produced in the same manner as in Example 7 except that the hole transporting polymer 3 was changed to the hole transporting polymer 2.

<Evaluation of organic EL elements>
When a voltage was applied to the organic EL elements obtained in Examples 7 to 12 and Comparative Examples 3 and 4, green light emission was confirmed in each of them. For each element, emission luminance 5,000 cd / ^{m 2} at the drive voltage and luminous efficiency were measured emission lifetime (luminance half-life) in the initial luminance 5,000 cd / ^{m 2.} The measurement results are shown in Table 4.

As shown in Table 4, the organic EL devices of Examples 7 to 12 showed a longer emission life than the organic EL devices of Comparative Examples 3 and 4. That is, from the viewpoint of the constituent material of the organic layer (lower layer), a polymer having no alkyl group having 5 or more carbon atoms and having an unsubstituted or thienyl group having an alkyl group having 1 to 4 carbon atoms at the end. It can be seen from (A) that the effect of improving the light emission life of the organic EL element can be obtained.

As described above, the effects of the embodiments of the present invention are shown by the examples. However, according to the present invention, not only the polymer (A) used in the examples, but also other polymers (A) and the initiator (B) are used as long as they do not deviate from the scope of the present invention. , It is possible to obtain an organic electronics element in the same manner. The obtained organic electronic device has excellent characteristics as in each embodiment.

1 Light emitting layer 2 Anode 3 Hole injection layer 4 Cathode 5 Electron injection layer 6 Hole transport layer 7 Electron transport layer 8 Substrate

Claims (13)

Polymer or oligomer (A), and contains an initiator for initiating the binding reaction between a thienyl group (B),
The polymer or oligomer (A) has a structural unit containing an aromatic amine structure and a terminal 1
One or more of them include a structural unit containing a thienyl group which may have a substituent and does not contain an alkyl group having 5 or more carbon atoms.
The structural unit containing the aromatic amine structure comprises a divalent structural unit containing an aromatic amine structure.
A composition whose solubility changes upon application of heat, light, or both heat and light. The composition according to claim 1, wherein the thienyl group comprises at least one selected from the group consisting of a structure represented by the following formula (Ia) and a structure represented by the following formula (Ib).

^{(R 1 to} R ³ in the formula (Ia) and the formula (Ib) are independently hydrogen atoms or carbon atoms 1.
Represents an alkyl group of ~ 4, and at least two of ^{R 1 to} R ^{3 are hydrogen atoms.} ) The polymer or oligomer (A) further comprises a structural unit comprising a carbazole structure.
The aromatic amine structure and the carbazole structure are unsubstituted or have 1 to 1 carbon atoms.
It has an alkyl group of 4 or an alkoxy group of 1 to 4 carbon atoms, or
The polymer or oligomer (A) does not contain a structural unit containing a carbazole structure, and the aromatic amine structure is unsubstituted, or an alkyl group having 1 to 4 carbon atoms or an alkoxy having 1 to 4 carbon atoms. The composition according to claim 1 or 2, which has a group. The invention according to any one of claims 1 to 3, wherein the polymer or oligomer (A) has a branched structure, has three or more ends, and has three or more thienyl groups at all ends. Composition. The composition according to any one of claims 1 to 4, wherein the initiator (B) contains an oxidizing agent. The composition according to any one of claims 1 to 5, wherein the initiator (B) contains an onium salt. The weight average molecular weight of the polymer or oligomer (A) is 1,000 to 1,000,0.
The composition according to any one of claims 1 to 6, which is 00. The composition according to any one of claims 1 to 7, further containing the solvent (C). The surface free energy represented by the Owens-Wendt method of the polymer or oligomer (A) as the sum of the two components of the polar component and the non-polar component is 41 mJ / m ² or more.
The composition according to any one of claims 1 to 8. A hole transport material composition containing the composition according to any one of claims 1 to 9. An ink composition containing the composition according to any one of claims 1 to 9. The composition according to any one of claims 1 to 9, the hole transport material composition according to claim 10, or the ink composition according to claim 11 is applied and heat, light, or heat is applied. An organic layer formed by the addition of both light. A step of applying the composition according to any one of claims 1 to 9, the hole transport material composition according to claim 10, or the ink composition according to claim 11 to form a coating layer. as well as,
A step of applying heat, light, or both heat and light to the coating layer.
A method for producing an organic layer, including.

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